Pure tungsten oxyphenolate complexes as DCPD polymerization catalysts

ABSTRACT

This invention relates to a two component catalyst system for polymerization of metathesis polymerizable cycloolefins, comprising 
     (a) a tungsten compound of the formula WOCl 4-x  (OAr) x  wherein Ar represents a hindered phenyl ring having bulky alkyl, alkoxyl halogen or aryl groups in the 2,6 position, i.e., diisopropyl or phenyl group and x=1, 2 or 3; and 
     (b) an activator compound that is triphenyl tin hydride or trialkyl tin hydride, preferably a tributyltin hydride. 
     Among the preferred molecules or groups that are substituted on the phenyl ring of the tungsten compound include chlorine, bromine, phenyl, methoxy and isopropyl. Ar may also represent a multisubstituted phenyl group such as 2,4-dichloro-6-methyl phenyl.

FIELD OF THE INVENTION

This invention is a process for the bulk polymerization of metathesispolymerizable cycloolefins, especially dicyclopentadiene, the polymerprepared by this process and the catalyst system used in the process.

BACKGROUND OF THE INVENTION

Preparation of thermoset cycloolefin polymers via metathesis catalystsis a relatively recent development in the polymer art. Klosiewicz, inU.S. Pat. Nos. 4,400,340 and 4,520,181, teaches preparation of suchpolymers from dicyclopentadiene and other similar cycloolefins via atwo-stream reaction injection molding technique wherein a first stream,including the catalyst, and a second stream, including a catalystactivator, are combined in a mix head and immediately injected into amold where, within a matter of seconds, polymerization and molding to apermanently fixed shape take place simultaneously.

In the typical system, according to Klosiewicz, the catalyst componentis a tungsten or molybdenum halide and the activator is an alkylaluminum compound. Most strained ring non-conjugated polycycliccycloolefins are metathesis polymerizable. These include, for example,dicyclopentadiene, higher order cyclopentadiene oligomers, norbornene,norbornadiene, 4-alkylidene norbornenes, dimethanooctahydronaphthalene,dimethanohexahydronaphthalene and substituted derivatives of thesecompounds. The preferred cyclic olefin monomer is dicyclopentadiene or amixture of dicyclopentadiene with other strained ring hydrocarbons inratios of 1 to 99 mole % of either monomer, preferably about 75 to 99mole % dicyclopentadiene.

The metathesis catalyst system is comprised of two parts, i.e., acatalyst component and an activator. The preferred catalyst component astaught by Klosiewicz has been a tungsten halide, and preferably amixture or complex of tungsten hexachloride (WCl₆) and tungstenoxytetrachloride (WOCl₄).

The tungsten or molybdenum compound of Klosiewicz is not normallysoluble in the cycloolefin, but can be solubilized by complexing it witha phenolic compound.

In U.S. application Ser. No. (315,075, filed Feb. 24, 1989, now U.S.Pat. No. 4,981,931) by Bell, was disclosed tungsten catalystcompositions for metathesis polymerization comprising ##STR1## where Xis Cl or Br, n is 2 or 3, R¹ is a H, a Cl, an alkyl group having 1-10carbons, an alkoxy group having 1 to 8 carbons, or a phenyl group, R² isH or an alkyl group having 1 to 9 carbon atoms and R³ is a H or an alkylgroup having 1 to 10 carbon atoms for use with a trialkyltin hydride ora triphenyltin hydride activator. A process to employ such tin activatorcompounds in a system in which gelation and polymerization were delayedfor at least a time sufficient to charge the reaction mixture to a mold.Both the catalyst and activator compounds had improved stability, withresistance to oxygen and moisture. The catalyst compounds were easy toisolate, instead of being mixtures as are those found in the prior art.Although certain advantages were found, these compounds when used topolymerize strained ring cycloolefins produced polymers with a higherthan desired residual monomer level.

It is therefore an object of this invention to provide a catalystcomposition that polymerizes strained ring polycyclic cycloolefins thathave very low levels of residual monomer.

There is also a need for polymers of the type described by Klosiewicz tohave higher levels of heat resistance, while maintaining otherproperties, such as impact and tensile strengths at levels similar tothose found in prior art strained ring cycloolefin polymers. Previously,improved heat resistance was obtained through use of comonomers with thedicyclopentadiene (DCPD) monomer. The improved heat resistance waspreviously obtained at the cost of decreased impact resistance.Therefore it is a further object of this invention to provide catalystcompositions that polymerize strained ring polycyclic cycloolefinsproducing polymers with a higher level of heat resistance than prior artpolymers while maintaining their impact strength.

Another object of this invention is to find catalysts that are moreefficient in polymerizing dicyclopentadiene.

This invention is a process for preparing a polymer which comprisescontacting a strained ring polycyclic polyolefin with a substantiallypure tungsten complex, having the formula WOCl_(4-x) (OAr)_(x) whereinOAr represents a mono-, di-, tri-, tetra- or penta- substituted phenoxygroup and where x is 1, 2 or 3. These catalysts are efficient andpromote catalysis of dicyclopentadiene at catalyst concentration levelsof 1 part catalyst to 4000 parts monomer or less.

Various activator compounds may be employed as are known in the art toact together with the tungsten catalyst complexes described above tocause the polymerization of strained ring polycyclic cycloolefins. Amongthe activator compounds that can be employed in the practice of thisinvention are trialkyltin hydrides, triaryltin hydrides, diethylaluminumchloride, diethylzinc, dibutylzinc, and triethylsilane. Mixtures of twoor more activator compounds may produce more desirable polymerizationconditions and more desirable polymer properties than a single activatorcompound in certain situations.

Of the trialkyl tin hydrides, suitable for use in the process of theinvention, tri-n-butyltin hydride is preferred. Among thetriaryltinhydrides is triphenyltin hydride.

As stated already hereinbefore the DCPD monomer used herein was ofhighly pure grade, containing less than 2% impurities. The DCPD used inthe following examples was about 98-99% pure monomer. Other monomers orcomonomers employed in the practice of this invention should also be ofabout this degree of purity. However, it is also contemplated that thepolymerization feed compositions of this invention can polymerize lesspure grades of dicyclopentadiene when the appropriate tungsten catalystcompound, activator compound and other components are employed.

When the two parts of the catalyst system, the tungsten catalyst and thetin activator, are combined, the resulting cycloolefin (for example,DCPD) to catalyst compound ratio will be from about 500:1 to about15,000:1 on a molar basis, preferably 2000:1 and the molar ratio of thetungsten complex versus the tin activator compound will be from about1:2 to 1:6.

Generally the polymerization takes place in bulk, but the catalystcomponents may be dissolved in a small amount of solvent, such astoluene. It is preferred, however, to use DCPD as a solvent. When theliquid tri-n-butyltin hydride activator compound is used, no solvent isnecessary for its addition and triphenyltin hydride is readily solublein DCPD.

A preferred method in the practice of this invention for thepolymerization of DCPD is to contact a tungsten compound catalystcomponent stream with a tin compound activator component stream whereinat least one of the streams contains the DCPD. For example, it ispossible to dissolve the tungsten catalyst in DCPD and either todissolve the activator in DCPD or in another solvent or to use theactivator without any solvent. Usually both the tungsten catalyst andthe tin activator are first dissolved in separate streams of DCPD priorto the mixture of said streams.

After the streams have contacted with each other the resulting mixturemay be injected or poured into a mold, where the polymerization takesplace. The polymerization is exothermic, but heating the mold from about50° to 100° C. is preferred.

The tungsten catalyst may be stored in DCPD for some time, provided thatthe DCPD contains only a few ppm of water or less. The tin activatorcompounds are storable in DCPD for prolonged periods and toleraterelatively higher levels of water than the catalysts without losingtheir activity. During the polymerization of DCPD various additives canbe included in the reaction mixture to modify the properties of thepolymer product of the invention. Possible additives include fillers,pigments, antioxidants, light stabilizers, plasticizers and polymericmodifiers.

The invention further relates to a two component catalyst system,comprising

(a) a tungsten compound of the formula WOCl_(4-x) (OAr)_(x) wherein Arrepresents a hindered phenyl ring substituted with bulky alkyl groupscontaining 1-10 carbon atoms, alkyl ketone or ester groups, carboxylgroups, alkoxyl groups, halogens or aryl groups, i.e., diisopropyl orphenyl groups, represented by R below and x=1, 2 or 3. Among thepreferred molecules or groups that are substituted on the phenyl ringinclude chlorine, bromine, iodine, phenyl, methoxy, CHO, COOCH₃, COR'(where R' is any of the groups that can be substituted on the phenylring as represented by R) and isopropyl. The substituents need not beidentical on a particular phenyl ring. For example, a trisubstitutedphenyl group such as 2,4-dichloro-6-methyl phenyl. A generalized formulato take the case of the mixed substituents into consideration is, e.g.,WOCl_(p) (OAr)_(q) (OAr)_(r) where p+q+r=4 Monodi, tetra, and pentasubstituted phenols can also be employed in making the tungstencompounds employed in this invention. The desired tungsten compounds areprepared by reacting the appropriate phenol with WOCl₄ in solution. Themolar ratio of phenol to WOCl₄ is about equal to x in the generalizedformula WOCl_(4-x) (OAr)_(x). The invention is also contemplated toinclude the use of mixtures of two or more different tungsten compounds.The phenyl ring, symbolized by Ar in the above general formula may haveR substituted at the 2,3, or 4 positions. In the disubstituted phenylring the substituents R₁ and R may be at the 2,6; 2,5; 2,4 or 2,3positions or at the 3,2; 3,4; 3,5 or 3,6 positions. R and R₁ may be thesame or different groups. In the trisubstituted phenyl ring substituentsR, R₁ and R₂ may be at the 1,3,5; 2,3,4; or the 3,4,5 positions, whereR, R₁ and R₂ may be the same or different. The two tetra substitutedstructures for the phenyl ring have substituents at the 2,3,5,6 or the2,3,4,5 positions, where R, R₁, R₂ and R₃ may be the same or different.An example of such would be made from 2,3,5,6-tetrachlorophenol. Thepenta substituted ring has substituents at the 2,3,4,5 and 6 positions,where each substituent may be the same or different. An example of thepenta substituted structure would be made from C₆ F₅ OH. and

(b) an activator compound that is triphenyltin hydride or trialkyltinhydride such as a tributyltin hydride. The phenyl group of the tungstencompound may have other substituents. Alkyl and phenyl zinc compounds,triethylsilane (in combination with a trialkytin hydride, alkylaluminumcompounds, alkylalkoxyaluminum halides and dialkylaluminum halides mayalso be employed.

In order to maintain the stability of tungsten compounds of the presentinvention with the 98-99% dicyclopentadiene without premature gelation,it is usually necessary to add a stabilizer compound to the solutioncontaining the tungsten compound, and a rate moderator to the solutioncontaining the tin activator compound. It is preferred to store thetungsten compounds in solution in dicyclopentadiene. When the stabilizercompound is omitted, a slow polymerization of the monomer proceeds inthe storage container. Stabilizer compounds include diethylether (OEt₂);ethyleneglycoldimethylethers (glyme), bis(methoxy)ethylether (diglyme),benzonitrile, acetonitrile, tetrahydrofuran, bulky phenols (such as2,6-di-t-butyl-4-methyl phenol (BHT)), bisphenols such as4,4'-methylenebis(2,6-dimethylphenol) (sold under the tradename Lowinox44M26), or 2,2'-methylene(4-methyl-6-t-butyl phenol) (sold under thetradename Vulkanox BKF) or polyphenols such as1,3,5-trimethyl-2,4-6-tris(3,5-di-t-butyl-4-hydroxybenzene) benzene(sold under the tradename Ethanox 330) may also be used. In addition,mixtures of the above stabilizer compounds such as a mixture of diglymeand one or more phenols or other Lewis bases can be employed in thepractice of this invention. The stabilizer compound prevents suchpolymerization from occurring until the addition of the activatorcompound. The rate moderator compound prevents the polymerizationprocess from being too rapid, provides for adequate mixing of thecatalyst components, and allows the mold to be completely filled. Therate moderator compounds include various nitrogen or phosphoruscompounds used for this purpose as described in U.S. Pat. Nos.4,727,125; 4,883,849; and 4,933,402. Preferred rate moderators includepyridine (py); pyrazine (pyz); tributylphosphine (Bu₃ P);tributylphosphite (TBP); triisopropylphosphite (TIPP);2,6-dimethylpyrazine (Me₂ pyz). The more preferred rate moderators arephosphines and phosphites, e.g., tributylphosphine (PBu₃) andtributylphosphite ((BuO)₃ P). The stabilizer and rate moderatorcompounds are not necessary when lower purity dicyclopentadiene isemployed, unless prolonged storage times are desired. Also, thestabilizer is not necessary when prolonged storage of the catalyst inthe monomer is not desired.

In some embodiments of this invention, a preformed elastomer which issoluble in the reactant streams is added to the metathesis-catalystsystem in order to increase the impact strength of the polymer. Theelastomer is dissolved in either or both of the reactant streams in anamount from about 3 to about 15 weight percent range, based on theweight of monomer. Illustrative elastomers include natural rubber, butylrubber, polyisoprene, polybutadiene, polyisobutylene, ethylenepropylenecopolymer, styrene-butadiene-styrene triblock rubber, randomstyrene-butadiene rubber, styrene-isoprene-styrene triblock rubber,ethylene-propylene-diene terpolymers, ethylene vinylacetate, and nitrilerubbers. Various polar elastomers can also be employed. The amount ofelastomer used is determined by its molecular weight and is limited bythe viscosity of the resultant reactant streams. The resultant reactantstreams containing elastomer cannot be so viscous that mixing is notpossible. Although the elastomer can be dissolved in either one or bothof the streams, it is desirable that it be dissolved in both.

In addition to measuring gel and cure times and residual DCPD monomerlevel, a measurement of swell value was made. The swell value is anindication of the degree of crosslinking in the polymer, i.e., lowerswell values indicate higher degree of crosslinking. The generalprocedure used for swell value determinations is as follows: A 5 gramsample of polymer is removed from its test tube (by breaking the glass)and carefully sliced into 1-2 mm thick sections across the cylindricalaxis with a tile cutter. The burrs are removed, each slice weighed tothe nearest milligram and strung onto a stainless steel or copper wiretaking care to keep them in known sequence. This is done for each sampleat a given monomer feed. The wire is made into a closed loop and placedin 50 ml of toluene for each gram of polymer. These flasks are thenheated to reflux for 16 hours (overnight) and cooled. Each loop issuccessively removed from the flask and placed in a small dish of freshtoluene. The slices are removed, patted dry, and weighed individually,again taking care not to disturb their sequence or to tear the swollensamples. The swell values are calculated using the following formula:swell (%)=(w₂ -w₁)/w₁ ×100%, where w₁ =initial weight of polyDCPD sampleand w₂ =weight of solvent swollen polyDCPD sample. Since the swell valueis an indication of the degree of crosslinking in the polymer, lowvalues are preferred.

The best mode now contemplated of carrying out this invention will beillustrated with the following examples. The examples are given for thepurpose of illustration only and the invention is not to be regarded aslimited to any of the specific materials or conditions used in theexamples.

In the following examples, in which tungsten complex catalyst componentsare prepared, tungsten hexachloride (WCl₆) was obtained from GTESylvania Chemical Company and used as received. 2,6-diisopropylphenoland 2,6-dichlorophenol (HOC₆ H₃ -2,6-Cl₂) were purchased from AldrichChemical Company and used as received. Hexamethyldisiloxane (Me₃SiOSiMe₃) (Aldrich) was sparged with dry nitrogen before use.

Cyclopentane, diethyl ether, and pentane were dried over 4A molecularsieves and sparged with nitrogen prior to use. Toluene was placed incontact with 13X molecular sieves and sparged with dry nitrogen beforeuse.

All operations were carried out under a dry nitrogen atmosphere or invacuum either in a Vacuum Atmospheres Dri-Lab (inerted by argon gas) orusing Schlenk techniques. All solvent transfers must be performed bycannula or syringe techniques to maintain an inert atmosphere.

In the Examples in which polymerization studies are set forth, thefollowing general procedures were followed. All manipulations wereperformed anaerobically in nitrogen-sparged pop bottles or under anargon atmosphere (Vacuum Atmospheres Dri-Lab) or using Schlenktechniques. Tri-n-butyltin hydride (packaged in Sure/Seal bottle) waspurchased from Aldrich Chemical Company and stored refrigerated (0° C.).Diglyme was dried by placing it over 3A molecular sieves and spargedwith nitrogen before use. Where necessary rate moderators, such astributylphosphite (Albright and Wilson), were dried over molecularsieves and sparged with dry nitrogen prior to use.

Polymerizations were conducted in nitrogen-sparged test tubes by addingtogether the catalyst and activator components (2.5 ml of each), mixingon a vortex mixer and then inserting the tube into an oil bath at 80° C.or higher or into a heated block at about 33° C. Gel times wereestimated by observing the initial viscosity change and the times weretaken when the polymerization raise the exotherm to 100° C. or 180° C.,and to the maximum temperature of the polymerization. Polymer swellswere obtained by refluxing the samples in toluene for 16 hours, coolingfor four hours and determining the percentage weight gain.

The tungsten starting material used in all catalyst preparation istungsten oxytetrachloride complex (WOCl₄). This compound was prepared inthe following manner. A solution of hexamethyldisiloxane (HMDS) (13.40ml, 0.063 mol) in toluene (100 ml) was added dropwise into a toluene(200 ml) solution of WCl₆ (25 g; 0.063 mol) in a 500 ml round bottomedflask (with stirring) over a 75 minute period. After the HMDS additionwas completed, the column was removed and the reaction mixture wasallowed to stir overnight under nitrogen. The brown solution wasfiltered in the dry box to yield a quantity of crude, orange WOCl₄(19.02 g; 88% yield). Immediately before use, the crude material wassublimed under reduced pressure at 100° C. in small portions to givebright orange crystalline WOCl₄. Pure commercial quantities of WOCl₄ maybe substituted in any of the catalyst preparations.

EXAMPLE 1

A tungsten phenoxide catalyst having the formula WOCl₂ (OC₆ H₃-2,6-i-Pr₂)₂ was prepared in the following manner. The addition of twomoles of the phenol for each mole of WOCl₄ produced the desired tungstenphenoxide compound. A quantity of WOCl₄ (5 g; 0.0146 moles) was placedin a pop bottle together with a stir bar. Toluene (50 mL) was added tothe WOCl₄ by cannula followed by the dropwise addition of neat2,6-diisopropylphenol (HOC₆ H₃ -2,6-i-Pr₂) (5.42 mL; 0.0296 mol). Thereaction mixture was allowed to stir at room temperature for three daysunder a nitrogen sparge. After this time, the reaction mixture was takeninto the dry box, scraped from the bottle, and further dried underreduced pressure. The complex WOCl₂ (OC₆ H₃ -2,6-i-Pr₂)₂ (8.83 g; 97%yield) was obtained as a dark purple solid.

Alternatively the catalyst may be prepared in accordance with thefollowing procedure: To a quantity of WOCl₄ (5 g; 0.0146 moles) stirringin cyclopentane (100 mL) was added dropwise a solution of2,6-diisopropylphenol (HOC₆ H₃ -2,6-i-Pr₂) (5.42 mL; 0.0296 mol) incyclopentane (50 mL). The dropwise addition of the phenolic solution wasaccomplished over a period of 30 minutes. During the phenol addition,the solution changed from orange to deep red. The reaction was allowedto stir at room temperature for two hours. After this time, the reactionmixture was taken in the dry box and filtered. No solids were collectedand the filtrate was evaporated to dryness under reduced pressure. Thecomplex WOCl₂ (OC₆ H₃ -2,6-i-Pr₂)₂ (8.22 g; 90% yield) was obtained as acrystalline dark purple solid.

EXAMPLE 2

A tungsten phenoxide catalyst having the formula WOCl₃ (OC₆ H₃ -2,6-Cl₂)was made by mixing WOCl₄ (3.79 g; 0.0111 moles) in cyclopentane (50 ml).A dropwise solution of 2,6-dichlorophenol (1.18 g ml; 0.111 mole) incyclopentane (25 ml) was then added dropwise over a period of 30minutes. During the phenol addition the solution changed color fromorange to deep red and purple crystals precipitated from the reactionsolution. The reaction was allowed to stir at room temperature for twohours. After this time the reaction mixture was taken into the dry boxand filtered. The solids collected by filtration were washed with 10 mlof pentane and dried in vacuum yielding 4.20 g (81%). The filtrate wasevaporated to dryness under reduced pressure and was determined to bethe same complex as the solid. The complex obtained, WOCl₃ (OC₆ H₃-2,6-Cl₂) was obtained as a dark red-purple solid. Other WOCl₃ (OAr)compounds can be prepared by substitution of other phenols for2,6-dichlorophenol.

EXAMPLE 3

A quantity (3.5 g; 7.475 mmol) of the product of Example 2 was used tomake a tungsten phenoxide compound having the formula WOCl₂ (OC₆ H₃-2,6-Cl₂)₂. Said quantity was dissolved in a minimum quantity of diethylether (50 ml) A saturated solution of lithium 2,6-dichlorophenoxide(LiOC₆ H₃ -2,6-Cl₂) (1.28 g ml; 7.58 mmol) in diethyl ether (about 8 ml)was slowly added dropwise. Almost instantly, the deposition of redcrystals occurred. The reaction mixture was stirred at room temperaturewith a slow nitrogen purge over the ether solution for 150 minutes.After an additional one hour of stirring, the reaction mixture wasfiltered to remove a dark red crystalline WOCl₂ (OC₆ H₃ -2,6-Cl₂)₂. Thesolid was then washed with a small volume of dried pentane (5 ml) andthe solid dried under vacuum (3.90 g). This material was dissolved indichloromethane (about 25 ml) and filtered to remove the lithiumchloride by-product. Evaporation of the filtrate under reduced pressureled to pure product in 72% yield (3.21 g).

EXAMPLE 4

In Example 4, stock solutions of the catalyst mixtures were prepared bycharging a ten ounce pop bottle with the appropriate measure of WOCl₃(OC₆ H₃ -2,6-Cl₂) prepared according to the process of Example 2 (ashorthand for referring to the tungsten catalyst compound in thisexample and in the following examples is "W"), DCPD and diglyme (DG).The activator solution was prepared by mixing tri-n-butyltin hydride(n-Bu₃ SnH); the appropriate quantity of tributylphosphite (TBP) andDCPD in a 10 ounce pop bottle. The following table indicates the amountsof materials used in preparing these two solutions.

    __________________________________________________________________________    Reaction Ratio A-Component B-Component                                        DCPD:W:DG:n-Bu.sub.3 SnH:TBP                                                                 DCPD:n-Bu.sub.3 SnH:TBP                                                                   DCPD:W:DG                                          __________________________________________________________________________    2000:1:2:2:3   1000:2:3    1000:1:2                                                          50 mL:0.39 mL:0.60 mL                                                                     50 mL:0.172 g:0.11 mL                              2000:1:2:2:3   1000:3:3    1000:1:2                                                          50 mL:0.59 mL:0.60 mL                                                                     50 mL:0.172 g:0.11 mL                              __________________________________________________________________________

The final reaction ratio for mixed catalyst and activator componentsvaried DCPD:W:diglyme:n-Bu₃ SnH:TBP=2000:1:2:2:3 to 2000:1:2:3:3 (seeTable 1)

                                      TABLE 1                                     __________________________________________________________________________    DCPD Polymerization By WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2)/n-Bu.su    b.3 SnH Mixtures                                                                          Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                                 DCPD:W:DG:Sn:TBP                                                                          (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                     __________________________________________________________________________    2000:1:2:2:3                                                                              30  1  8   13  26  206                                                                              78.8                                                                              0.09                                    2000:1:2:2:3                                                                              30  1  7   13  29  206                                                                              --  --                                      2000:1:2:2:3                                                                              80  1  8   13  26  210                                                                              85.0                                                                              0.25                                    2000:1:2:3:3                                                                              30  1  4   11  24  195                                                                              --  --                                      2000:1:2:3:3                                                                              30  1  4   10  22  203                                                                              79.2                                                                              0.12                                    2000:1:2:3:3                                                                              80  1  5   12  26  207                                                                              82.7                                                                              0.23                                    __________________________________________________________________________

EXAMPLE 5

In Example 5 the catalyst stock solution was prepared by charging a 10oz pop bottle with the appropriate amount of WOCl₂ (OC₆ H₃ -2,6-Cl₂)₂,DCPD and DG. Stock solutions of the activator were prepared by charginga 10 oz pop bottle with the appropriate amounts of n-Bu₃ SnH and TBP.The following table indicates the amounts of materials used.

    __________________________________________________________________________    Reaction Ratio A-Component B-Component                                        DCPD:W:DG:n-Bu.sub.3 SnH:TBP                                                                 DCPD:n-Bu.sub.3 SnH:TBP                                                                   DCPD:W:DG                                          __________________________________________________________________________    2000:1:2:2:3   1000:3:2    1000:1:2                                                          100 mL:0.39 mL:0.40 mL                                                                    100 mL:0.44 g:0.22 mL                              4000:1:2:2:3   2000:3:2    2000:1:2                                                          100 mL:0.20 mL:0.20 mL                                                                    100 mL:0.22 g:0.11 mL                              8000:1:2:2:3   4000:3:2    4000:1:2                                                          100 mL:0.10 mL:0.10 mL                                                                    100 mL:0.11 g:0.05 mL                              2000:1:2:3:3   1000:3:2    1000:1:2                                                          100 mL:0.59 mL:0.59 mL                                                                    100 mL:0.44 g:0.22 mL                              4000:1:2:3:3   2000:3:2    2000:1:2                                                          100 mL:0.30 mL:0.30 mL                                                                    100 mL:0.22 g:0.11 mL                              8000:1:2:3:3   4000:3:2    4000:1:2                                                          100 mL:0.15 mL:0.15 mL                                                                    100 mL:0.11 g:0.05 mL                              __________________________________________________________________________

The final reaction ratio for mixed catalyst and activator components wasvaried from DCPD:W:diglyme:n-Bu₃ SnH:TBP=2000:2:8:3 to 8000:1:2:8:3 (seeTable 2).

                                      TABLE 2                                     __________________________________________________________________________    DCPD Polymerization By WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2      /n-Bu.sub.3 SnH Mixtures                                                      Effect of DCPD:WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2 Ratio On     Residual DCPD Levels                                                                      Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                                 DCPD:W:DG:Sn:TBP                                                                          (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                     __________________________________________________________________________    2000:1:2:2:3                                                                              30  10 32  38  51  208                                                                              79.0                                                                              0.04                                    2000:1:2:2:3                                                                              80  8  17  22  34  208                                                                              90.5                                                                              0.09                                    4000:1:2:2:3                                                                              33  6  22  27  40  208                                                                              76.5                                                                              0.07                                    4000:1:2:2:3                                                                              80  8  16  22  36  211                                                                              85.7                                                                              0.21                                    8000:1:2:2:3                                                                              33  7  33  36  51  209                                                                              76.7                                                                              0.17                                    8000:1:2:2:3                                                                              80  6  21  28  39  192                                                                              91.3                                                                              0.57                                    2000:1:2:3:3                                                                              30  8  25  31  43  204                                                                              80.6                                                                              0.11                                    2000:1:2:3:3                                                                              80  8  17  21  32  212                                                                              94.9                                                                              0.16                                    4000:1:2:3:3                                                                              33  4  21  27  39  207                                                                              80.0                                                                              0.12                                    4000:1:2:3:3                                                                              80  4  16  22  37  215                                                                              91.6                                                                              0.22                                    8000:1:2:3:3                                                                              33  5  23  29  42  204                                                                              75.6                                                                              0.40                                    8000:1:2:3:3                                                                              80  5  19  24  38  209                                                                              90.0                                                                              0.44                                    __________________________________________________________________________

EXAMPLE 6

In Example 6 the catalyst stock solution was prepared by charging a 10oz pop bottle with the appropriate amount of WOCl₂ (OC₆ H₃ -2,6-i-Pr₂)₂,DCPD and diglyme. Stock solutions of the activator were prepared bycharging a 10 oz pop bottle with the appropriate amounts of n-Bu₃ SnHand tributylphosphite ((TBP). The following table indicates the amountsof materials used.

    __________________________________________________________________________    Reaction Ratio A-Component B-Component                                        DCPD:W:DG:n-Bu.sub.3 SnH:TBP                                                                 DCPD:n-Bu.sub.3 SnH:TBP                                                                   DCPD:W:DG                                          __________________________________________________________________________    2000:1:2:1:3   1000:1:3    1000:1:2                                                          100 mL:0.20 mL:0.60 mL                                                                    100 mL:0.44 g:0.22 mL                              2000:1:2:2:3   1000:2:3    1000:1:2                                                          100 Ml:0.40 mL:0.60 mL                                                                    100 mL:0.44 g:0.22 mL                              2000:1:2:3:3   1000:3:2    1000:1:2                                                          100 mL:0.59 mL:0.60 mL                                                                    100 mL:0.44 g:0.22 mL                              2000:1:2:6:3   1000:6:3    1000:1:2                                                          100 mL:1.18 mL:0.60 mL                                                                    100 mL:0.44 g:0.22 mL                              2000:1:2:8:3   1000:8:3    1000:1:2                                                          100 mL:1.58 mL:0.60 mL                                                                    100 mL:0.44 g:0.22 mL                              __________________________________________________________________________

The final reaction ratio for mixed catalyst and activator components wasvaried from DCPD:W:diglyme:n-Bu₃ SnH:TBP=2000:1:2:1:3 to 2000:1:2:8:3(see Table 3).

                                      TABLE 3                                     __________________________________________________________________________    DCPD Polymerization By WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2      /n-Bu.sub.3 SnH Mixtures:                                                     Effect of DCPD:WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2 /n-Bu.sub    .3 SnH Ratio On Residual DCPD Levels                                                      Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                                 DCPD:W:DG:Sn:TBP                                                                          (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                     __________________________________________________________________________    2000:1:2:1:3                                                                              33  15 50  55  70  210                                                                              88.1                                                                              0.12                                    2000:1:2:1:3                                                                              80  12 29  41  49  190                                                                              103.8                                                                             2.04                                    2000:1:2:2:3                                                                              33  8  30  34  46  208                                                                              90.8                                                                              0.06                                    2000:1:2:2:3                                                                              80  7  19  22  34  211                                                                              102.1                                                                             0.12                                    2000:1:2:3:3                                                                              30  8  25  31  43  204                                                                              80.6                                                                              0.11                                    2000:1:2:3:3                                                                              80  8  17  21  32  212                                                                              94.9                                                                              0.16                                    2000:1:2:6:3                                                                              33  1  13  17  30  200                                                                              94.9                                                                              0.30                                    2000:1:2:6:3                                                                              80  1  12  17  29  210                                                                              109.5                                                                             0.38                                    2000:1:2:8:3                                                                              34  1  10  16  29  211                                                                              97.6                                                                              0.54                                    2000:1:2:8:3                                                                              80  1  10  16  29  202                                                                              103.1                                                                             0.50                                    __________________________________________________________________________

EXAMPLE 7

In Example 7 the stock solution of the catalyst was prepared by mixingthe appropriate amounts of WOCl₂ (OC₆ H₃ -2,6-i-Pr₂)₂, DCPD and DG in a10 oz pop bottle. Activator stock solutions were prepared by charging a10 oz pop bottle with the appropriate amounts of n-Bu₃ SnH and TBP. Thefollowing table indicates the amounts of materials used.

The final reaction ratio for mixed catalyst and activator components wasvaried from DCPD:W:diglyme:n-Bu₃ SnH:TBP=2000:1:2:3:0 to 2000:1:2:3:4(see Table 4)

EXAMPLE 8

In Example 8, various Lewis bases were used to delay polymerization witha WOCl₂ (OC₆ H₃ -2,6-i-Pr₂)₂ catalyst compound and n-Bu₃ SnH activatorcompound. Among the Lewis bases were tributylphosphite ((BuO)₃),pyridine (py); 2,6-dimethylpyridine (2,6-Me₂ py); pyrazine (pyz),2,6-dimethylpyrazine (2,6-Me₂ pyz); triisopropylphosphite (i-PrO)₃ P;dibutylphosphite (BuO)₂ P(O)H) and tributylphosphine (Bu₃ P). The samegeneral polymerization procedure was employed as was previouslyexplained herein. The proportions of dicyclopentadiene (DCPD): tungstencatalyst (W):diglyme (DG):trin-butyltin hydride (Sn):Lewis base (LB) isshown in the results that are shown in Table 5.

    __________________________________________________________________________    Reaction Ratio A-Component B-Component                                        DCPD:W:DG:n-Bu.sub.3 SnH:TBP                                                                 DCPD:n-Bu.sub.3 SnH:TBP                                                                   DCPD:W:DG                                          __________________________________________________________________________    2000:1:2:3:2   1000:3:2    1000:1:2                                                          100 mL:0.59 mL:40 mL                                                                      100 mL:0.50 g:0.21 mL                              2000:1:2:3:3   1000:3:3    1000:1:2                                                          100 mL:0.59 mL:0.59 mL                                                                    100 mL:0.50 g:0.21 mL                              2000:1:2:3:4   1000:3:4    1000:1:2                                                          100 mL:0.59 mL:0.79 mL                                                                    100 mL:0.50 g:0.21 mL                              2000:1:2:3:8   1000:3:8    1000:1:2                                                          100 mL:0.59 mL:1.59 mL                                                                    100 mL:0.50 g:0.21 mL                              __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    DCPD Polymerization By WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2      /n-Bu.sub.3 SnH Mixtures:                                                     Effect of DCPD:WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2 /TBP         Ratio On Residual DCPD Levels                                                             Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                                 DCPD:W:DG:Sn:TBP                                                                          (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                     __________________________________________________________________________    2000:1:2:3:2                                                                              33  5  16  21  33  207                                                                              91.4                                                                              0.10                                    2000:1:2:3:2                                                                              33  4  18  23  35  208                                                                              --  --                                      2000:1:2:3:2                                                                              80  5  14  18  30  210                                                                              102.9                                                                             0.15                                    2000:1:2:3:2                                                                              80  4  14  19  31  207                                                                              --  --                                      2000:1:2:3:3                                                                              30  8  25  31  43  204                                                                              80.6                                                                              0.11                                    2000:1:2:3:3                                                                              30  8  29  34  47  205                                                                              --  --                                      2000:1:2:3:3                                                                              80  8  17  21  32  212                                                                              94.9                                                                              0.16                                    2000:1:2:3:3                                                                              80  8  17  21  37  215                                                                              --  --                                      2000:1:2:3:4                                                                              33  9  31  37  49  207                                                                              96.0                                                                              0.15                                    2000:1:2:3:4                                                                              33  9  33  38  49  199                                                                              --  --                                      2000:1:2:3:4                                                                              80  8  18  23  36  212                                                                              111.1                                                                             0.27                                    2000:1:2:3:4                                                                              80  9  19  24  36  213                                                                              --  --                                      2000:1:2:3:4                                                                              33  16 63  66  80  206                                                                              96.7                                                                              0.17                                    2000:1:2:3:8                                                                              33  19 66  72  85  202                                                                              --  --                                      2000:1:2:3:8                                                                              80  13 25  31  45  217                                                                              106.8                                                                             0.26                                    2000:1:2:3:8                                                                              80  14 24  30  45  217                                                                              --  --                                      __________________________________________________________________________

                                      TABLE 5                                     __________________________________________________________________________    Activation of WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.2 By          n-Bu.sub.3 SnH: Effect of Various Lewis Bases                                             Lewis  Initial                   Residual                                     Base   Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                          DCPD:W:DG:Sn:TBP                                                                          (LB)   (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                              __________________________________________________________________________    2000:1:2:3:3                                                                              (BuO).sub.3 P                                                                        30  7  23  28  41  206                                                                              75.9                                                                              0.35                             2000:1:2:3:3                                                                              (BuO).sub.3 P                                                                        80  9  24  30  45  211                                                                              95.5                                                                              0.33                             2000:1:2:3:3                                                                              py     31  90 319 --  345 175                                                                              160.4                                                                             0.39                             2000:1:2:3:3                                                                              py     80  40 53  57  78  212                                                                              145.2                                                                             0.63                             2000:1:2:3:3                                                                              2,6-Me.sub.2 py                                                                      30  1  15  21  33  204                                                                              94.1                                                                              0.37                             2000:1:2:3:3                                                                              pyz    30  14 331 --  275 175                                                                              176.9                                                                             0.34                             2000:1:2:3:3                                                                              pyz    80  10 49  52  65  211                                                                              162.2                                                                             0.77                             2000:1:2:3:3                                                                              2,6-Me.sub.2 pyz                                                                     30  12 60  69  85  198                                                                              147.0                                                                             0.39                             2000:1:2:3:3                                                                              2,6-Me.sup.2 pyz                                                                     80  10 32  37  48  208                                                                              143.0                                                                             0.49                             2000:1:2:3:3                                                                              (i-PrO).sub.3 P                                                                      30  14 25  30  47  210                                                                              71.8                                                                              0.29                             2000:1:2:3:3                                                                              (-PrO).sub.3 P                                                                       80  10 15  22  38  204                                                                              82.0                                                                              0.65                             2000:1:2:3:3                                                                              (BuO).sub.2 P(O)H                                                                    31  44 86  91  108 205                                                                              91.9                                                                              0.31                             2000:1:2:3:3                                                                              (BuO).sub.2 P(O)H                                                                    80  22 31  39  58  212                                                                              98.4                                                                              0.68                             2000:1:2:3:3                                                                              Bu.sub.3 P                                                                           80  100                                                                              120 128 140 220                                                                              115.8                                                                             0.63                             __________________________________________________________________________

EXAMPLE 9

In Example 9, the effect of various Lewis bases upon polymerization andthe polymer produced was conducted with WOCl₂ (OC₆ H₃ -2,6-Cl₂)₂tungsten phenoxide catalysts and tri-n-butyltin hydride activator. Theabbreviations in the following Table 6 are the same as explained inExample 8.

EXAMPLE 10

In Example 10 the effect of tributylphosphine upon polymerization whenusing a WOCl₂ (OC₆ H₃ -2,6-i-Pr₂)₂ (example 1) catalyst was determined.The effect upon polymerization is seen in Table 7.

EXAMPLE 11

In Example 11 a similar comparison of the effect of tributylphosphinewas conducted as in Example 9 with WOCl₂ (OC₆ H₃ -2,6-Cl₂)₂ as thetungsten catalyst. The results are shown in Table 8.

                                      TABLE 6                                     __________________________________________________________________________    Activation of WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2 By            n-Bu.sub.3 SnH: Effect of Various Lewis Bases                                             Lewis  Initial                   Residual                                     Base   Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                          DCPD:W:DG:Sn:TBP                                                                          (LB)   (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                              __________________________________________________________________________    2000:1:2:3:3                                                                              (BuO).sub.3 P                                                                        30  7  25  31  47  207                                                                              82.1                                                                              0.12                             2000:1:2:3:3                                                                              (BuO).sub.3 P                                                                        80  7  20  24  40  212                                                                              994.1                                                                             0.20                             2000:1:2:3:3                                                                              py     30  120                                                                              254 268 282 198                                                                              91.7                                                                              0.35                             2000:1:2:3:3                                                                              py     80  29 36  39  55  219                                                                              114.8                                                                             0.26                             2000:1:2:3:3                                                                              pyz    30  1  33  42  58  195                                                                              98.9                                                                              0.37                             2000:1:2:3:3                                                                              2,6-Me.sup.2 pyz                                                                     30  8  31  41  48  188                                                                              88.6                                                                              0.50                             2000:1:2:3:3                                                                              2,6-Me.sup.2 pyz                                                                     80  5  16  24  35  200                                                                              94.1                                                                              0.43                             2000:1:2:3:3                                                                              (-PrO).sub.3 P                                                                       30  1  134 19  31  203                                                                              78.1                                                                              0.17                             2000:1:2:3:3                                                                              (BuO).sub.2 P(O)H                                                                    30  66 202 212 230 200                                                                              87.3                                                                              0.13                             2000:1:2:3:3                                                                              (BuO).sub.2 P(O)H                                                                    80  23 30  33  47  213                                                                              90.6                                                                              0.23                             2000:1:2:3:3                                                                              Bu.sub.3 P                                                                           80  90 123 129 140 230                                                                              95.3                                                                              0.28                             __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________    Polymerization Using WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.2      /n-Bu.sub.3 SnH: Effect of                                                    Tributylphosphine (Bu.sub.3 P)                                                            Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                                 DCPD:W:DG:Sn:Bu.sub.3 P                                                                   (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                     __________________________________________________________________________    2000:1:2:3:1                                                                              80  56 73  76   90 223                                                                              --  --                                      2000:1:2:3:1                                                                              80  55 76  78  100 229                                                                              129.8                                                                             1.36                                    2000:1:2:3:2                                                                              80  76 98  102 118 224                                                                              145.5                                                                             0.66                                    2000:1:2:3:2                                                                              80  70 93  98  116 222                                                                              --  --                                      2000:1:2:3:3                                                                              80  100                                                                              120 128 248 220                                                                              115.8                                                                             0.63                                    2000:1:2:3:3                                                                              80  100                                                                              124 128 150 228                                                                              120.6                                                                             0.96                                    __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________    Polymerization Using WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Cl.sub.2).sub.2      /n-Bu.sub.3 SnH: Effect of                                                    Tributylphosphine (Bu.sub.3 P)                                                            Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                                 DCPD:W:DG:Sn:Bu.sub.3 P                                                                   (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                     __________________________________________________________________________    2000:1:2:3:1                                                                              32  81 160 163 177 205                                                                              83.9                                                                              0.17                                    2000:1:2:3:1                                                                              32  150                                                                              218 223 235 202                                                                              --  --                                      2000:1:2:3:1                                                                              80  24 30  46  60  215                                                                              --  --                                      2000:1:2:3:1                                                                              80  30 40  46  64  222                                                                              89.1                                                                              0.24                                    2000:1:2:3:2                                                                              80  74 84  87  112 227                                                                              --  --                                      2000:1:2:3:2                                                                              80  66 84  87  103 233                                                                              93.3                                                                              0.35                                    2000:1:2:3:3                                                                              80  90 123 129 140 230                                                                              95.3                                                                              0.28                                    2000:1:2:3:3                                                                              80  114                                                                              136 140 159 232                                                                              --  --                                      __________________________________________________________________________

EXAMPLES 12-13

In Examples 12 and 13 various activators are used to the tributyltinhydride used in the previous examples. Among the activators tested weretriphenyltin hydride (Ph₃ SnH), diethylaluminum chloride (Et₂ AlCl),diethylzinc (DEZ), diisobutylzinc (DIBZ), and ethyl-n-propoxyaluminumchloride(Et(n-Pro)AlCl) (ENPAC). Example 12 employed the diisopropylsubstituted tungsten compound of Example 1, and in Table 9 are seen theactivators that worked to polymerize the DCPD monomer.

In Example 12 the tungsten compound of Example 3 was used with variousactivator compounds. Table 10 shows the results of DCPD polymerizationwith such activators.

EXAMPLE 14

Polymerization of dicyclopentadiene was completed utilizing WOCl₃ (OAr)catalysts and n-Bu₃ SnH. The WOCl₃ (OAr) catalysts were prepared inaccordance with the general procedure of Example 2.

EXAMPLES 15-16

In Examples 15 and 16 the activator used was a mixture of tri-n-butyltinhydride and triethylsilane (Et₃ SiH). The tungsten compound of Example 1was used in the polymerizations of Example 15, the results of which areshown in Table 11. The tungsten compound of Example 3 was used in thepolymerizations of Example 16, the results of which are shown in Table12.

                                      TABLE 9                                     __________________________________________________________________________    DCPD Polymerization Utilizing Various Activators In Combination with          WOCl.sub.2 (OC.sub.6 H.sub.3 2,6-i-Pr.sub.2).sub.2                                             Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                            DCPD:W:DG:Sn:Act                                                                         Activator                                                                           (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                __________________________________________________________________________    2000:1:2:3:3                                                                             n-Bu.sub.3 SnH*                                                                     30  7  23  28  41  206                                                                              75.9                                                                              0.35                               2000:1:2:3:3                                                                             n-Bu.sub.3 SnH*                                                                     80  9  24  30  45  211                                                                              95.5                                                                              0.33                               2000:1:2:3:3                                                                             Ph.sub.3 SnH                                                                        30  1  27  31  48  210                                                                              65.6                                                                              0.28                               2000:1:2:3:3                                                                             Ph.sub.3 SnH                                                                        80  1  26  30  45  214                                                                              76.1                                                                              0.73                               2000:1:2:3:3                                                                             Ph.sub.3 SnH*                                                                       80  40 79  84  98  229                                                                              83.7                                                                              0.58                               2000:1:2:3:3                                                                             Et.sub.2 AlCl                                                                       30  1  160 169 190 193                                                                              58.1                                                                              0.55                               2000:1:2:3:3                                                                             Et.sub.2 AlCl                                                                       80  2  44  47  61  220                                                                              --  --                                 2000:1:2:3:3                                                                             Et.sub.2 AlCl**                                                                     80  16 147 159 168 212                                                                              69.3                                                                              2.04                               2000:1:2:3:3                                                                             DIBZ**                                                                              80  25 1.5 245 260 196                                                                              92.9                                                                              1.71                               __________________________________________________________________________     *Addition of one mole equivalent of tributylphosphite (TBP) per mole of       activator.                                                                    **Addition of one mole equivalent of diglyme (DG) per mole of activator. 

                                      TABLE 10                                    __________________________________________________________________________    DCPD Polymerization Utilizing Various Activators In Combination with          WOCl.sub.2 (OC.sub.6 H.sub.3 2,6-i-Pr.sub.2).sub.2                                             Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                            DCPD:W:DG:Sn:Act                                                                         Activator                                                                           (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                __________________________________________________________________________    2000:1:2:3:3                                                                             n-Bu.sub.3 SnH*                                                                     30  7  19  25  41  209                                                                              94.1                                                                              0.12                               2000:1:2:3:3                                                                             n-Bu.sub.3 SnH*                                                                     80  4  18  24  39  209                                                                              82.1                                                                              0.20                               2000:1:2:3:3                                                                             Ph.sub.3 SnH                                                                        30  1  74  85  99  200                                                                              --  --                                 2000:1:2:3:3                                                                             Ph.sub.3 SnH                                                                        80  1  30  34  48  214                                                                              110.0                                                                             0.27                               2000:1:2:3:3                                                                             Ph.sub.3 SnH*                                                                       80  72 172 182 200 222                                                                              114.9                                                                             1.10                               2000:1:2:3:3                                                                             Et.sub.2 AlCl**                                                                     30  12 104 114 130 202                                                                              67.7                                                                              1.8                                2000:1:2:3:3                                                                             Et.sub.2 AlCl**                                                                     80  9  35  39  48  207                                                                              89.1                                                                              2.9                                2000:1:2:3:3                                                                             ENPAC 80  90 279 282 300 239                                                                              126.1                                                                             0.41                               2000:1:2:3:3                                                                             DEZ** 25  1  7   13  23  193                                                                              --  --                                 2000:1:2:3:3                                                                             DIBZ**                                                                              30  1  19  25  36  205                                                                              --  --                                 2000:1:2:3:3                                                                             DIBZ**                                                                              28  1  29  33  50  208                                                                              --  --                                 2000:1:2:3:3                                                                             DIBZ**                                                                              80  1  24  27  46  209                                                                              --  --                                 __________________________________________________________________________     *Addition of one mole equivalent of tributylphosphite (TBP) per mole of       activator.                                                                    **Addition of one mole equivalent of diglyme (DG) per mole of activator. 

                                      TABLE 11                                    __________________________________________________________________________    Reactivity of WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.2 with        Different Ratios                                                              of Tri-n-Butyltin Hydride and Triethylsilane                                                Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                               Activator     (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                   __________________________________________________________________________    75% n-Bu.sub.3 SnH: 25% Et.sub.3 SiH                                                        30  12 33  37  53  209                                                                              104.1                                                                             0.09                                  75% n-Bu.sub.3 SnH: 25% Et.sub.3 SiH                                                        80   9 24  28  44  215                                                                              105.6                                                                             0.28                                  50% n-Bu.sub.3 SnH: 50% Et.sub.3 SiH                                                        30  15 58  64  80  202                                                                               87.1                                                                             0.11                                  50% n-Bu.sub.3 SnH: 50% Et.sub.3 SiH                                                        80  11 27  31  46  213                                                                               93.8                                                                             0.31                                  25% n-Bu.sub.3 SnH: 75% Et.sub.3 SiH                                                        30  28 --  --  300 56 --  --                                    25% n-Bu.sub.3 SnH: 75% Et.sub.3 SiH                                                        80  15 --  --  300 88 --  --                                    __________________________________________________________________________

                                      TABLE 12                                    __________________________________________________________________________    Reactivity of WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2 with          Different Ratios                                                              of Tri-n-Butyltin Hydride and Triethylsilane                                                Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                               Activator     (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                   __________________________________________________________________________    75% n-Bu.sub.3 SnH: 25% Et.sub.3 SiH                                                        30  10 29  33  52  210                                                                              83.9                                                                              0.07                                  75% n-Bu.sub.3 SnH: 25% Et.sub.3 SiH                                                        80   9 19  23  39  218                                                                              94.3                                                                              0.19                                  50% n-Bu.sub.3 SnH: 50% Et.sub.3 SiH                                                        30  12 46  51  68  199                                                                              82.7                                                                              0.05                                  50% n-Bu.sub.3 SnH: 50% Et.sub.3 SiH                                                        80  10 22  27  44  217                                                                              90.8                                                                              0.18                                  25% n-Bu.sub.3 SnH: 75% Et.sub.3 SiH                                                        30  19 102 109 120 202                                                                              90.2                                                                              0.3                                   25% n-Bu.sub.3 SnH: 75% Et.sub.3 SiH                                                        80  16 39  44  59  213                                                                              83.9                                                                              0.98                                  __________________________________________________________________________

EXAMPLES 17-18

WOCl₂ (OAr)₂ catalysts were prepared in accordance with analogousprocedures to those disclosed in Example 3, substituting the appropriatephenol for that disclosed in Example 3. The results of polymerizationwith these catalysts is shown in Table 13.

WOCl₃ (OAr) catalysts were prepared in accordance with analogousprocedures to those disclosed in Example 2. The results ofpolymerization with these catalysts is shown in Table 14.

EXAMPLE 19

In examining the synthesis of WOCl₂ (OC₆ H₃ -2,6-i-Pr₂)₂ (Example 1), itwas found that WOCl(OC₆ H₃ -2,6-i-Pr₂)₃ can be generated in the reactionpot at ambient temperature. Pure WOCl(OC₆ H₃ -2,6-i-Pr₂)₃ can only besynthesized by the addition of one mol. equivalent of lithium2,6-diisopropylphenoxide in diethyl ether at -30° C. At 80° C., WOCl(OC₆H₃ -2,6-i-Pr₂)₃ can be activated by tri-n-butyltin hydride (n-Bu₃ SnH)to generate a polymerizing species (Table 15). No polymerizationexotherm was observed at room temperature. The 2,6-dichlorophenol analogto the above 2,6-dichlorophenol substituted tungsten compound WOCl(OC₆H₃ -2,6-Cl₂)₃, was found to be much more easily activated by n-Bu₃ SnH,so polyDCPD was formed at room temperature as well as at more typicalmolding temperatures.

                                      TABLE 13                                    __________________________________________________________________________                   Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                              Catalyst       (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                  __________________________________________________________________________    WOCl.sub.2 (OC.sub.6 H.sub.2 -2,4-Cl.sub.2 -6-Me).sub.2                                      31  11 24  33  51  196                                                                              64.2                                                                              0.44                                 WOCl.sub.2 (OC.sub.6 H.sub.2 -2,4-Cl.sub.2 -6-Me).sub.2                                      80  10 21  26  41  209                                                                              75.1                                                                              0.66                                 WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Ph.sub.2).sub.2                                            30  15 38  43  60  203                                                                              121.3                                                                             0.16                                 WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Ph.sub.2).sub.2                                            80  11 21  27  39  202                                                                              137.9                                                                             0.29                                 __________________________________________________________________________     The above polymerizations were run at the following ratios:                   DCPD: W: DG: Sn: TBP                                                          2000: 1: 2: 3: 3                                                         

                                      TABLE 14                                    __________________________________________________________________________                 Initial                   Residual                                            Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                                                                        Swell                                                                             Monomer                                Catalyst     (°C.)                                                                      (sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                                                                     (%) (%)                                    __________________________________________________________________________    WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-Br.sub.2)                                                30  5  15  22  40  205                                                                              72.5                                                                              0.10                                   WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-Br.sub.2)                                                80  4  12  18  36  209                                                                              79.9                                                                              0.23                                   WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-OMe.sub.2)                                               31  40 84  89  105 208                                                                              68.5                                                                              0.28                                   WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-OMe.sub.2)                                               80  15 23  30  46  218                                                                              86.2                                                                              0.58                                   __________________________________________________________________________     The above polymerizations were run at the following ratios:                   DCPD: W: DG: Sn: TBP                                                          2000: 1: 2: 3: 3                                                         

                                      TABLE 15                                    __________________________________________________________________________    Polymerization Data for WOCl(OAr).sub.3 /n-Bu.sub.3 SnH Mixtures:             Effect of Temperature and Rate Moderator                                                         Initial                                                                       Temp.                                                                             t.sub.gel                                                                        t.sub.100° C.                                                              t.sub.180° C.                                                              tT.sub.max                                                                        T.sub.max                               WOCl(OAr).sub.3 Catalyst                                                                   W:Sn:TBP                                                                            (°C.)                                                                      (Sec)                                                                            (sec)                                                                             (sec)                                                                             (sec)                                                                             (°C.)                            __________________________________________________________________________    WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3                                               1:3:0 31  1  no polymerization at 420s                           WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3                                               1:3:0 80  1  224 231 243 214                                     WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3                                               1:3:0 80  1  211 219 239 225                                     WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3                                                 1:3:0 31  1  23  27  42  205                                     WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3                                                 1:3:0 31  1  29  37  53  206                                     WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3                                                 1:3:0 80  1  21  29  41  201                                     WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3                                                 1:3:0 80  1  22  29  42  194                                     WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3                                               1:3:3 80  11 96  105 115 214                                     WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3                                               1:3:3 80  13 87  93  107 221                                     WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3                                               1:3:3 80  13 85  92  109 223                                     WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3                                                 1:3:3 31  8  59  66  78  199                                     WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3                                                 1:3:3 31  8  60  64  82  208                                     WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3                                                 1:3:3 80  7  28  31  46  219                                     WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3                                                 1:3:3 80  7  28  32  47  214                                     __________________________________________________________________________     Overall reaction ratio DCPD:W procatalyst:diglyme:nBu.sub.3 SnH =             2000:1:2:3)                                                              

EXAMPLE 20

In this example, the tungsten catalyst compositions of Examples 1-4 wereused to mold 98-99% pure DCPD in combination with tri-n-butyltinhydride, moderated by tributylphosphite in a 3.5% Royalene 301T(ethylene-propylene-diene monomer (EPDM)) rubberized formulation. Whenthe catalyst of Example 1 was used, parts were produced with 1.2%residual monomer. The reaction ratio was DCPD:W:DG:n-Bu₃SnH:TBP=2000:1:2:3:2. The properties were comparable to prior artformulations, except that the heat distortion temperature (HDT) wassignificantly higher than has been found except when a quantity oftricyclopentadiene or some other monomers were added to the DCPDmonomer. The HDT was found to be about 117°-118° C., more than 15° C.than the control. The addition of the antioxidant Irganox 1035 did notaffect the Notched Izod value, but reduced the heat distortiontemperature by about 6° C. The addition of 10% of tricyclopentadiene(Cp-trimer) to the formulation resulted in a further 8° C. boost in HDT.More importantly, the Notched Izod value remained high compared to priorart compositions, even after aging. A sample of this rubberizedmaterial, containing no antioxidant, was aged at 70° C. and the changein Notched Izod as a function of time was recorded. After four days, theNotched Izod had plateaued at about 5.0 ft. lb./in. as compared to priorart material which had a Notched Izod value of about 2.5 ft lb/in afteraging.

A pure tungsten catalyst having the formula WOCl₂ (OC₆ H₃ -2,6-Cl₂)₂ wasprepared in accordance with the procedure of Example 3 and whenactivated by tri-n-butyltin hydride an extremely active catalystsolution was produced for the polymerization dicyclopentadiene. At80°/60° C. molding temperatures, a 3.5% Royalene 301T rubberized DCPDsolution (DCPD:W:Sn=2000:1:3) was polymerized by WOCl₂ (OC₆ H₃-2,6-Cl₂)₂ (stabilized by two molar equivalents of diglyme) incombination with n-Bu₃ SnH (moderated by two equivalents oftributylphosphite (TBP)) to yield poly(DCPD) containing only 0.37%residual DCPD and having a high heat distortion temperature of 118° C.WOCl₃ (OC₆ H₃ -2,6-Cl₂) was prepared in accordance with the procedure ofexample 2. The catalyst system produced was very fast in gelling andcuring DCPD. For example, at proportions of DCPD:W:DG:n-Bu₃ SnH: TBP of2000:1:2:3:3 at 30° C., t_(gel) was less than 1 second, t₁₀₀° C. was 4seconds and t₁₈₀° C. was 10 seconds. It was found possible to preparepolyDCPD plaques having very low levels of residual monomer (0.28%) andexcellent properties (Table 13). The heat distortion temperature of 123°C. is a very high level. Table 16 shows the properties of parts moldedin accordance with the above description.

                                      TABLE 16                                    __________________________________________________________________________                      Tensile    Flex             HDT  Residual                                                                            Tg                                Modulus                                                                            Strength                                                                           Elongation                                                                          Modulus                                                                            Strength                                                                           Notched Izod                                                                         (264 psi)                                                                          Monomer                                                                             (DMA)                Sample       (Kpsi)                                                                             (Kpsi)                                                                             (%)   (Kpsi)                                                                             (Kpsi)                                                                             (ftlb/in)                                                                            (°C.)                                                                       (wt %)                                                                              (°C.)         __________________________________________________________________________    Example 1 Catalyst                                                                         249.0                                                                              5.5  28.0  277.4                                                                              9.8  11.7   117  1.2   154                  (2 eq. DG/2 eq. TBP)                                                          Example 1 Catalyst                                                                         --   --   --    --   --   11.7   111  0.86  --                   (2 eq. DG/2 eq. TBP)                                                          2% Irganox 1035                                                               Example 1 Catalyst                                                                         237.6                                                                              5.9  37.9  283.1                                                                              9.8  7.6    125  1.3   165                  (2 eq. DG/2 eq. TBP)                                                          10% Cp-trimer Monomer                                                         Example 3 Catalyst                                                                         237.6                                                                              5.9  37.1  252.0                                                                              8.9  9.1    118  0.38  148                  (2 eq. DG/2 eq. TBP)                                                          Example 3 Catalyst                                                                         250.4                                                                              6.7  66.6  280.3                                                                              10.0 9.1    123  0.28  146                  (2 eq. DG/2 eq. TBP)                                                          __________________________________________________________________________     In all cases, reaction ratio used is DCPD:W:Sn = 2000:1:3.                    Diglyme (DG) is added as a catalyst stabilizer. Tributlyphosphite (TBP) i     added as a rate modifier.                                                     ***3.5% Royalene 301T.                                                   

We claim:
 1. A polymerization feed composition comprising:(a) ametathesis polymerizable cycloolefin; (b) a metathesis polymerizationcatalyst represented by the formula WOCl_(4-x) (OAr)_(x) ; wherein x is1, 2 or 3, wherein OAr represents a mono-, di-, tri-, tetra- orpenta-substituted phenoxy group, and (c) a catalyst activator.
 2. Thepolymerization feed composition of claim 1 wherein said catalystactivator is selected from the group consisting of alkylaluminumcompounds, alkylalkoxyaluminum halides, dialkylaluminum halides,trialkyltin hydrides, triaryltin hydrides, a mixture of trialkyltinhydrides and triethylsilane, dialkylzinc and diphenylzinc compounds. 3.The polymerization feed composition of claim 2, wherein said catalystactivator is tri-n-butyltin hydride.
 4. The polymerization feedcomposition of claim 1 wherein said cycloolefin is a monomer selectedfrom the group consisting of dicyclopentadiene, higher ordercyclopentadiene oligomers, norbornene, norbornadiene, 4-alkylidenenorbornenes, dimethanohexahydronaphthalene,dimethanohexahydronaphthalene, or a mixture of two or more of saidmonomers.
 5. The polymerization feed composition of claim 2, whereinsaid cycloolefin is dicyclopentadiene.
 6. The polymerization feedcomposition of claim 1 wherein said Ar in said metathesis polymerizationcatalyst is a phenyl ring, wherein said ring is substituted with alkyl,alkoxy, ketone, ester, carboxyl or aryl groups or halogens or mixturesthereof.
 7. The polymerization feed composition of claim 16 wherein saidphenyl ring is substituted with substituents selected from the groupconsisting of chlorine, bromine, iodine, phenyl, methyl, methoxy, andisopropyl groups.
 8. The polymerization feed composition of claim 6wherein said substituents are substituted at one or more positions onsaid phenyl ring wherein said positions are selected from the groupconsisting of the 2 position, the 3 position, the 4 position, the 2,6positions, the 2,5 positions, the 2,4 positions, the 2,3 positions, the3,2 positions, the 3,4 positions, the 3,5 positions, the 3,6 positions,the 2,4,6 positions, the 2,3,4 positions, the 3,4,5 positions, the2,3,5,6 positions, the 2,3,4,5 positions and the 2,3,4,5,6 positions. 9.The polymerization feed composition of claim 1 further comprising a ratemoderator compound.
 10. The polymerization feed composition of claim 9wherein said rate moderator compound is selected from the groupconsisting of pyridine, pyrazine, tributylphosphine,triisopropylphosphite, 2,6-dimethylpyrazine, and tributylphosphite. 11.The polymerization feed composition of claim 1 wherein said metathesispolymerization catalyst further comprises a stabilizer compound.
 12. Thepolymerization feed composition of claim 11 wherein said stabilizercompound is a Lewis base.
 13. The polymerization feed composition ofclaim 11 wherein said stabilizer compound is selected from the groupconsisting of diethylether; ethyleneglycoldimethylethers,bis(methoxy)ethylether, benzonitrile, acetonitrile, tetrahydrofuran,bulky phenols, bisphenols, polyphenols and mixtures thereof.
 14. Thepolymerization feed composition of claim 13 wherein said stabilizercompound is bis(methoxy)ethyl ether.
 15. The polymerization feedcomposition of claim 14 wherein said stabilizer compound furthercomprises a phenol.
 16. A process for preparing molded objectscomprising charging to a mold a liquid reaction mass comprising ametathesis polymerizable cycloolefin, a metathesis polymerizationcatalyst, and a catalyst activator, wherein said catalyst is representedby the formula WOCl_(4-x) (OAr)_(x) wherein x is 1, 2 or 3 and Ar is aphenyl ring having between 1-5 substituents and wherein after saidliquid reaction mass is charged to said mold, said reaction masspolymerizes in said mold.
 17. The process of claim 16 wherein saidcatalyst activator is selected from the group consisting ofalkylaluminum compounds, alkylalkoxyaluminum halides, dialkylaluminumhalides, trialkyltin hydrides, triaryltin hydrides, a mixture oftrialkyltin hydrides and triethylsilane, dialkylzinc and diphenylzinccompounds.
 18. The process of claim 17 wherein said catalyst activatoris tri-n-butyl tin hydride.
 19. The process of claim 16 wherein saidcycloolefin is a monomer selected from the group consisting ofdicyclopentadiene, higher order cyclopentadiene oligomers, norbornene,norbornadiene, 4-alkylidene norbornenes, dimethanohexahydronaphthalene,dimethanohexahydronaphthalene, or a mixture of two or more of saidmonomers.
 20. The process of claim 19 wherein said cycloolefin isdicyclopentadiene.
 21. The process of claim 16 wherein said phenyl ringis substituted with alkyl, alkoxyl, ketone, ester, carboxyl or arylgroups or halogens or mixtures thereof.
 22. The process of claim 21wherein said phenyl ring is substituted with a substituent selected fromthe group consisting of chlorine, bromine, iodine, phenyl, methyl,methoxy, and isopropyl groups.
 23. The process of claim 21 wherein saidsubstituents are substituted at one or more positions on said phenylring wherein said positions are selected from the group consisting ofthe 2 position, the 3 position, the 4 position, the 2,6 positions, the2,5 positions, the 2,4 positions, the 2,3 positions, the 3,2 positions,the 3,4 positions, the 3,5 positions, the 3,6 positions, the 2,4,6positions, the 2,3,4 positions, the 3,4,5 positions, the 2,3,5,6positions, the 2,3,4,5 positions and the 2,3,4,5,6 positions.
 24. Theprocess of claim 16 further comprising a rate moderator compound. 25.The process of claim 16 wherein said rate moderator compound is selectedfrom the group consisting of pyridine, pyrazine, tributylphosphine,triisopropylphosphite, 2,6-dimethylpyrazine, and tributylphosphite. 26.The process of claim 16 wherein said metathesis polymerization catalystfurther comprises a stabilizer compound.
 27. The process of claim 26wherein said stabilizer compound is a Lewis base.
 28. The process ofclaim 26 wherein said stabilizer compound is selected from the groupconsisting of diethylether; ethyleneglycoldimethylethers,bis(methoxy)ethylether, benzonitrile, acetonitrile, tetrahydrofuran,bulky phenols, bisphenols, polyphenols and mixtures thereof.
 29. Theprocess of claim 28 wherein said stabilizer compound isbis(methoxy)ethyl ether.
 30. The process of claim 29 wherein saidstabilizer compound further comprises a phenol.